Revealing principles of coordination self-assembly working under kinetic control

2023 Fiscal Year Final Research Report

• Project/Area Number: 21K18974
• Research Category: Grant-in-Aid for Challenging Research (Exploratory)
• Allocation Type: Multi-year Fund
• Review Section: Medium-sized Section 34:Inorganic/coordination chemistry, analytical chemistry, and related fields
• Research Institution: The University of Tokyo
• Principal Investigator: Hiraoka Shuichi 東京大学, 大学院総合文化研究科, 教授 (10322538)
• Co-Investigator(Kenkyū-buntansha): 高橋 聡 東京大学, 大学院総合文化研究科, 助教 (20456180)
• Project Period (FY): 2021-07-09 – 2024-03-31
• Keywords: 分子自己集合 / 速度論支配 / 自己集合経路 / 反応ネットワーク / 準安定状態

Outline of Final Research Achievements

In this study, we investigated the principle of kinetically controlled self-assembly for the MnLm self-assembly systems consisting of a metal ion (M) and a multidentate ligand (L). A mathematical model of the reversible reaction network was constructed, and numerical simulations of titrating M against L were performed, which gave highly stable M4L4 cyclic assembly via selective formation of MxLX+1 chain intermediates, resulting in higher yields than those in the equilibrium state. This result was also verified experimentally in the MnLm system. Next, experimental and theoretical investigations of the self-assembled system of the M6L4 truncated tetrahedron revealed that the M6L4 assembly was formed through a four-membered ring intermediate and that this pathway was selected because of the emergence of irreversibility in certain elementary reactions in the reaction network.

Free Research Field

超分子化学・分子自己集合

Academic Significance and Societal Importance of the Research Achievements

一般的に可逆反応は熱力学支配により化学平衡へ至る。このような場合、反応の帰結は反応経路に依存しない。本研究では各素反応が可逆であっても、これらが連結した反応ネットワークを構築すると、速度論の影響を受けることが明らかとなり、その原理の一端が解き明かされたことで、自然界に見られる速度論支配による自己集合の意義やその理解といった基礎学理への寄与に加えて、本研究で明らかになった原理に基づく新たな物質合成の新手法の開発へ繋がると期待される。